manufacture of thickened



Patented June ll-9 34 1 ACTURE F rmcnanan. BODIED OIL PRODUCTS FROM FATTY OILS Laszl Auer and Lajos Susztek, Budapest, Hungary No Drawing. Application April 21, 1930, Serial No. 446,173. in

30 Claims.

This invention relates to the manufacture of thickened, bodied oil products from fatty oils, and it comprises methods of making such oil products wherein certain soaps are dissolved or dispersed in the said fatty oil, advantageously by heating a mixture of the fatty oil and soap to temperatures sufficient to effect a thickened or bodying of the oil, the temperatures being advantageously about 200 C. or higher, until said oil in the present inas tung oil, linseed oil, fish oils (train oils), poppyseed oil, sunflower oil, cottonseed oil, rapeseed oil, soya bean oil, pine oil, corn oil, olive oil, castor oil, etc. Products containing the acids of fatty oils may also be used.

This invention is particularly adaptable to making the said oil products from drying oils; linseed oil and the like.

By the previous investigations of one of us, Laszld Auer, there has been developed various methods of producing thickened, bodied oil products from fatty oils and the like, with the aid of certain polar compounds or electrolytes (called modifying agents) under a wide range of conditions; all of those methods involve changes in the lsocolloid system of the fatty oil. The oil products so obtained are thickened, modified fatty oils. Such modifying agents are e. g. salts of organic and inorganic acids, metallic derivatives of organic compounds, certain organic acids, compounds comprising within the molecule an acidic inorganic residue and an organic residue: By an acidic'inorganlc residue we mean such an inorganic residue as can be converted by the addition of one or more hydrogen atoms into an inorganic acid (including carbonic acid as inorganic). It will be seen that this definition includes such compounds as organic halogen derivatives (e. g. trichloroacetic acid, chloral hydrate, iodoform, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, mono-chloracetic acid,

4-chloro-o-anisidine, pinene hydrochloride,

naphthalene tetrachloride, p-nitrochlorobenzene,

benzyl chloride, triphenylchloro-methane, acetyl chloride, benzoyl chloride) organic sulphonic acids and their halides and esters, e. g.-

Great Britain April 24, 1929 Sodium 2 6 :8 naphthylaminedisulphonate Sodium 2 6: 8 naphtholdisulphonate Sodium 1 8 z 3 :6 aminonaphtholdisulphonate Sodium 1:5 naphtholsulphonate Sodium 2:3 :6 naphtholdisulphonate Sodium 2: 6 naphtholsulphonate Sodium 2:6 naphthylaminesulphonic acid Sodium 2:1 naphthylaminesulphonic acid 2-phenylamino-8-naphthol-6-6 sulphonic acid, Beta-naphthylamine 3:6:8 trisulphonic acid, Beta naphtol- 3 6 i 8 trisulphonic acid, Beta-naphthol 1:5 disulphonic acid, Naphthalene 2:6 disulphonic acid, Naphthalene 1 sulphonyl chloride, Alpha-naphthyl sulphamic acid,

m-xylidine sulphonic acid,

Benzene sulphonic acid,

p-toluene sulphonic acid,

p-toluene sulphonyl chloride,

5-sulpho salicylic acid,

p-toluldine m-sulphonic acid,

Benzene sulphonyl chloride,

2:5 dichlor benzene sulphonic acid,

methyl ester of p-toluene sulphonic acid, ethyl chlorsulphonate (esters of inorganic acids) e. g. 'dimethylsulphate, triphenyl or tricresyl phosphate, nitrocresol carbonates, and inorganic salts of organic bases e. g. m-nitroaniline hydrochloride, diaminodiphenylamine sulphate, aminoazo-benzene sulphate, diphenylamine hydrochloride, diphenyl-amine, hydrobromide, diphenylamine trichloracetate, trichloraniline hydrochloride.

Further examples are o-nitrophenol, p-nitrophenol, p-nitro acetanilide, dinitraniline, fluoresceine, eosin, thiocarbanilide, 4:4 -diaminodiphenyl sulphide, diphenyl sulphone. Further diphenylamine sulphate,

modifying agents are certain metallic peroxides,

e. g. peroxides of magnesium,zink, barium, strontium, calcium, sodium etc., alkali metals, their oxides and hydroxides etc. In certain cases more than one of the modifying agents may be used such, for instance, favorable results are obtained by treating the starting material with an alkali metal, its oxide or hydroxide and with a metal peroxide. Aromatic amines, especially diamines and amines with high molecular weight are also suitable modifying agents. The given list of modifying agents shall not be a complete one as other agents giving the desired results may be used for the said purpose.

The modifying agents starting material in a dry should be added to the form (without the presence of water) and-in relatively small quantities. In order to ensure complete dissolution or disper- .110

sion of the modifying agent, the operation of dissolving or dispersing the latter should be carried out under application of heat. The degree of heat necessary depends upon the nature of the substance under treatment and also of the modifying agent used. Generally temperatures from 100 to 300 C. or more will give satisfactory results. The heat treatment promotes the complete (molecular or colloidal) dissolution of the modifying agent in the substance to be treated. In some cases it may be advisable to continue the heat treatment after the dissolution or dispersion of the modifying agent is substantially complete.

It has been further found that the results of the process vary with the nature and/or with the physical condition (pressure) of the gas (air or other gas) present in the reaction chamber. Thus, it has been found that a certain given starting material which is initially liquid will become viscous only as the result of the electrolyte treatment, if the latter is effected under atmospheric pressure (e. g. in an open vessel), but solid if the gas is rarified by the employment of a partial vacuum. In other cases the converse applies. When plus pressure was used (e. 3. caused by the tension of the starting materials at higher temperatures), the results diifer again from both of those of the treatments under atmospheric pressure and vacuum. Also, as to the nature of the gas present, an" gives for in= stance a different result from another gas, or mixture of gases. The pressure conditions may also be alternated during the gas treatment which, of course may be carried out together with the dissolution or dispersion of the modifying agent in the substance to be treated or as an aftertreatment.

It may be stated with reference to the action of gases that generally speaking rarifaction or the gases present in the reaction chamber by reduction of pressure tends to intensify their action in the process both in the case of solidification of the starting material and also in the case of liquefaction thereof.

The gas treatment may be carried out by blowing the gas through the reaction mixture or simply by passing it over the mass contained in the reaction chamber. The gas may be further produced in situ in the reaction mass by using substances which under the conditions of the reaction develop gases as desired. Such, for instance by using peroxides, carbonates, sulphides, sulphites and the like the corresponding gases may v be developed in the reaction mass.

The process as described may be made to effect a solidification or a liquefaction of the initial material. Thus, for instance, thickened products and even solid substances like hard rubber may be obtained from thin oils. The results obtained depend in any given case upon the conditions of the reaction, e. g. upon the duration of the heat-treatment of the material, the duration of the gas-treatment, the quantity of the dissolved Generally speaking the products obtained were, from liquids, solid or semi-solid thermoplastic masses, and from solids,

pasty or thin liquids.

If desired, the modifying agentv may be produced in situ within the mass of the=substance under treatment by interaction within the substance, of substances capable of reacting under the conditions of the process to produce the modifying agent wanted.

The dissolution or dispersion of the modifying agents in .the starting material may be favorably iriiuenced by the addition of certain "auxiliary agents or sensitizers. These fall into two groups, namely the purely inorganic (e. g. silica gel, vfullers earth), and the purely organic (e. g. formaldehyde, phenol, thiocarbanilide, benzidine, hexamethylenetetramine, 2 :3-hydroxy-naphthoic acid, a-naphthol, quinoline, pyrogallol, benzene, glycerol and phthalimide). The specific examples of auxiliary agents here mentioned are to be taken as typical of the substances which have been successfully used for this purpose and not as comprising all the effective substances. It should be mentioned that quite a number of the modifying agents comprising within the molecule an acidic inorganic residue and an organic residue are auxiliary agents (sensitizers) when used in conjunction with other modifying agents. By an acidic inorganic residue we mean such an inorganic residue as can be converted by the addition of one or more hydrogen atoms, into an inorganic acid (includin carbonic acid as inorganic). Thus, e. g. the dissolution of 5% of sodium bisulphite in linseed oil is facilitated and the color of the product is'made lighter by the addition of say 2% of such compounds as aminoazobenzene sulphate, aniline sulphate, nitro cresyl carbonate, dimethyl sulphate, trichloroacetic acid, benzenesulphonicacid, iodoform, naphthalene tetrachloride, pinene hydrochloride, m-xylidinesulphonio acid, [i-naphthylamine-Sz'8-disulphonic acid, p-naphthylamine 6-sulphomc acid, acetyl chloride, p-nitroacetanilide, chloral hydrate, and triphenyl phosphate, naphthalene-sulphochloride, diphenyl-amine hydrobromide, 5 or 3-amino salicylic acid, 2:6-naphthalene disulphonic acid, 0- dichlorobenzene.

The advantages of a rapid dissolutionof the modifying agent are greatest in those cases where a clear, pale or colorless product is desired, especially' for example, for the varnish industry.

For the modification of the physical properties of the initial materials solutions or colloidal solutions of one or more electrolytes in an organic solvent may be used.

Solid coherent and elastic products may be obtained, similar in general characteristics to ordinary rubber, by adding sulphur to the initial sub= stance in addition to the agents already mentioned. The sulphur may be added as such or in the form of a sulphur compound (e. g. sulphur chloride) which under the conditions of the process decomposes with liberation of nascent sulphur. It would appear that the action of the sulphur is analogous to that which takes place in the vulcanization of rubber. The sulphur or sulphur compounds may be added either at the beginning of the process or so as to act only during the gas treatment part of the process. Alternatively, the sulphur or sulphur compounds may be added to the material after the main reaction of the process has been completed. Alternating treatment with sulphur dioxide and hydrogen sulphide has been found to be specially useful in certain cases. The vulcanizing treatment results carbamate, diethylammonium, diethyl-dithiocarbamate etc.) 'are added. vulcanization occurs below 100 C.

The modified materials produced by these processes may be used in a variety of industries, e. g.

described methods.

therewith,

in the rubber, linoleum, varnish, soap and candle industries and others.

A very important application of the new products is the manufacture of new artificial materials by emulsification of organic isocolloids. One of the emulsification processes consists in subjecting the isocolloid first to a treatment with modifying agents of the kind described and thereafter effecting further transformation by emulsification or dispersion in an aqueous medium. Or, the isocolloid may be first emulsified or dispersed in an aqueous medium and thereafter treated with one or more of the above characterized agents which are capable of modifying the physical properties of the starting material. The emulsions or dispersions may be vulcanized or sulphurized by one of the above sions obtained, whether vulcanized or not, are valuable in the art for a variety of purposes. They may be for example concentrated and used for impregnation of textiles; or the disperse phase may be separated in solid form by means of the usual coagulating agents, or by drying (as e. g. when the aqueous dispersions are used for varnishes), or it may be deposited in forms by dipping (in which case it is advantageous to cover the form with a coat containing a coagulant) or by electrophoresis; or the disperse phase may be separated from the dispersing medium by ultrafiltration. The emulsion may be used alone or in admixture with natural rubber latex or an artificially prepared emulsion of rubber, which may or may not have been previously vulcanized, in any or all of the above treatments, and for any of the purposes mentioned.

In all cases the treatment may be profitably influenced byexposing the materials undergoing treatment to oscillating energy (X-rays, ultraviolet rays, infrared rays etc.) or by including the reaction chamber in an electric circuit.

Filling materials, pigments and the like may be added at any stage of the processes.

In the case of most fatty oils the isocolloidal system does not contain a sufiiciently high concentration of the disperse phase to enable colloidal changes to take place, and for instance heating at higher temperatures is necessary to increase the concentration of the disperse phase. This heating frequently causes a darkening of the products and it is very desirable to devise methods which enable in all cases a modifying action at comparatively lower temperatures and with shorter heat treatment.

Such processes and products are described and claimed in the copending applications Ser. Nos. 143,786 and 359,425 filed by Laszlo Auer, one of the inventors.

The present inventions are improvements upon those processes and may be used in conjunction they being likewise based upon changes in the isocolloid system of the fatty oil.

We have now found that the addition of soaps of the alkali and alkaline earth metals and oi. zinc and magnesium to the isocolloids by dispersing or dissolving the former in the latter, brings about a modifying action at compartively low temperatures and with short treating periods.

The present invention accordingly comprises a process for the modification of fatty. oils, thickened, modified fatty oils and the like, wherein the modification is efiected' by dispersing or ing material by heating at comparatively low The emulsions or disper-l temperatures until a considerable modification of the physical properties of the starting material has been obtained. The above specified soaps act partly as modifying agents, partly as a new disperse phase in the system. The proportion of soaps to be added lies between 5 and 20% generally. In certain cases, however, satisfactory results can be obtained by using less than 5% or more than 20% of soaps.

The melting point of the product depends upon the quantity of the soap dissolved and to a smaller extent upon the duration of heating. It has been found that the dispersion of such soaps in the isocolloids to be treated can be very advantageously carried out by rubbing or kneading of the soaps into the material to be modified in the presence of water when the soap is water-soluble, or in the presence of an organic solvent when the soap is soluble in an organic solvent, for instance benzene. The rubbing or kneading is carried out generally at room temperatures, and after the water or organic solvent has been driven oif by drying the mixture, a modified product results without the use of heat to any considerable extent. Especially alkali soaps yield very light-colored products according to the present invention. Subsequent vulcanization leads to factice like products which show improved properties in rubber mixes, and the reaction product may be used either unvulcanized or vulcanized for varnish purposes. In the vulcanization, accelerators and/or activators may be used. Fillers or pigments may be incorporated at any stage into the reaction mass.

Besides unmodified isocolloids of the type described also those modifled by any method, described in said copending applications Ser. Nos. 143,786 and 359,425 may be used as starting materials for the process; the products of this double modification find application as raw materials for varnishes.

The modifying process according to the present invention may be carried out under the influence of radiations such as infra-red rays, ultra-violet rays, X-rays etc., or by making the reaction mass part of an electric circuit. The properties of the products may further be infinanced by concomitant or subsequent treatment with gases.

The following examples are given by way of 5 illustration and are in no way limitative. The parts are by weight.

Example 1 Example 2 100 parts linseed oil and 5 parts of the potassium soap of the acids of linseed oil, are heated for 1 hour at 200 C. The viscous mass resulting from the reaction is cooled to 16 C. and treated with 5 parts of sulphur chloride under constant stirring, yielding a very viscous, tacky,

oil product which can be advantageously used as varnish raw materials. When instead of potassium soap, a soap containing another metai tained.

Example 3 parts linseed oil and 5 parts sodium soap of the acids of linseed oil are heated for 40 minutes at 200 C. The product is cooled to 160 C. and vulcanized with the aid of 3 parts sulphur, 1 zinc oxide and 0.7 mercaptobenzthiazole, yielding a viscous oil product for varnish purposes.

. What we claim is:

1. As an improvement in the manufacture of thickened, heat-bodied oil products from fatty oils, the steps which comprise mixing together a fatty oil with a soap, said soap being a salt of fatty acids and a metal of the class consisting of alkali metals, alkaline earth metals, magnesium and zinc, and heating the mixture thus obtained, to a temperature of at least 200 C., untilv a thickened, heat-bodied oil product is obtained.

2. The process of claim 1 in which 5 to 20 parts of said soap are mixed with 100 parts of said fatty oil.

3. The process of claim 1 in which said fatty oil is linseed oil and said fatty acids are the fatty acids of linseed oil.

4. The process of claim 1 in which said soap is a soap of alkali metal.

5. The process of claim 1 in which said soap is a sodium soap.

6. The process of claim 1 in which said soap is a potassium soap.

'7. In the manufacture of thickened, heat-v bodied oil products from linseed oil, the process which comprises mixing together linseed oil with an alkali metal soap of theacids of linseed oil, heating the mixture to between 200 and 220 C., to distribute said soap in the linseed oil, the heating being continued until a thickened, bodied oil product is obtained and recovering the products thus produced.

8. In the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with between 5 to 20 parts of an alkali metal soap of the fatty acids of linseed oil, heating the mixture to about 200 C., to distribute said soap in the linseed oil, the heating being continued until a thickened, bodied oil product is obtained and recovering the products thus obtained.

9. The process of claim 8 in which 10 parts of the sodium soap of the fatty acids of linseed oil is used.

10. The process of claim Bin which 5 parts of potassium soap of the fatty acids of linseed oil is used.

11. Intthe manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing linseed oil with an alkali soap of thefatty acids of linseed oil, heat-, ing the mixture at a temperature su l cient to thicken and heat-body said mixture, the temperature being at least 200 C., until said thickened, heat-bodied oil product is produced, adding a vulcanizing agent to said thickened, heatbodied oil, heating to a temperature and for a time sufficient to effect vulcanization, and recovering the vulcanized, thickened, heat-bodied oil products thus obtained.

12. In the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with 10 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to between 200 and 220 C. for approximately one hour, cool is used, a somewhat different product is obing the mixture thus obtained, adding about 3 percent of sulphur and heating at 180 for about 'one hour and recovering the modified products thus obtained, said modified products being suitable as raw materials in the manufacture of varnish,

13.11: the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with 10 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to between 200 and 220 C. for approximately one hour, cooling the mixture thus obtained, adding about 10 per cent of sulphur and maintaining the mixture at about 180 C. until complete vulcanization is effected and recovering the modified products thus obtained, said modified products being useful as a rubber substitute.

14. In the manufacture of modified products from linseed oil, the process which comprises mixing together 100 parts of linseed oil and 5 parts of the potassium soap of the fatty acids of linseed oil, heating the mixture thus obtained at 200 C. for about one hour, cooling the viscous mass so obtained to about 16 C., reacting the cooled mixture thus obtained with about 5 parts of sulphur chloride, recovering the very vlscous tacky product thus obtained, said product being useful as a raw material in the manufacture of varnish.

15. In the manufacture of modified products from linseed oil, the process which comprises mixing 100 parts of linseed oil and 5 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to 200 C. for about 40 minutes, cooling the product thus obtained to about 160 C., mixing the cooled product with approximately 3 parts of sulphur, zinc oxide and mercaptobenzthiazole and heating the vulcanizable mass thus obtained at the vulcanizing temperature and recovering the viscous oily product thus obtained, said product being suitable in the manufacture of varnish.

16. As an improvement in the manufacture of vulcanized products from fatty oils, the process which comprises mixing together 100 parts of a fatty oil with between 5 to 20 parts of a soap,'

said soap being a salt of fatty acids and a metal of the class consisting of alkali metals, alkaline earth metals, magnesium and zinc, heating the mixture to a temperature of at least 200 C. until a thickened, bodied oil product is obtained, adding to the bodied oil thus obtained, a vulcanizing agent of the class consisting of sulphur and sulphur chloride, and then subjecting said mixsaidsoap being a salt of fatty acids and a metal 5 to 20 per cent of an alkali metal soap of the fatty acids of linseed oil, the said soap enhancing the body obtained by heat-bodying said oil.

20. As a new product, a non-oxidized, vulcanized, heat-bodied faty oil, heat-bodied at temperatures of at least 200 C., obtained from a mix ture of a fatty oil and a soap by the process of claim 16, the body of said oil being due partly to heat-bodying, partly to the presence of said soap and partly to vulcanization. V

21. As an improvement in themanufacture of thickened heat-bodied oil products from fatty oils, the process which comprises mixing a drying fatty oil with a soap, said soap being an alkali metal salt of the fatty acids of a drying fatty oil, heating the mixture at temperatures sufiicient to thicken and heat-body the same until .said thickened, heat-bodied oil products are produced, said temperature being at least 200 C.

22. As an improvement in the manufacture of vulcanized and thickened, heat-bodied oil products from fatty oils of the drying type, the two step process which comprises mixing a drying fatty oil with a soap, said soap being an alkali metal salt of the fatty acids of a drying fatty oil, heating the mixture at temperatures sufiicient to thicken and'heat-body the same until a thickened, heat-bodied oil is obtained, said temperature being at 200 C. and then mixing the bodied oil thus obtained with a vulcanizing agent and heating the mixture of bodied oil and vulcanizing agent to temperatures sufiicient to effect reaction and vulcanization and recovering the vulcanized and thickened heat-bodied oil product thus obtained.

23. As an improvement in the manufacture of oil products from drying oils, said oil products being suitable for making quick drying varnishes, the 2-step process which comprises mixing a soap with a drying fatty oil, heating the mixture to at least 200 C. until a thickened bodied oil is obtained and then mixing said thickened bodied oil with sulphur and a vulcanization accelerator, heating the vulcanizable mass thus obtained to vulcanizing temperatures and recovering said oil products.

24. As an improvement in the manufacture of bodied oil products from drying fatty oils, the'2- step process which comprises first producing a thickened bodied oil by mixing a drying fatty oil with alkali metal soap of the fatty acids of a drying oil and heating the mixture to at least 200 C. until a thickened bodied oil is produced, and then vulcanizingsaid thickened bodied oil by mixing said bodied oil with sulphur, an activator and a vulcanization accelerator and heating the vulcanizable mass thus obtained to vulcaniz temperatures, thereby producing said bodied oil products.

25. As an improvement in the manufacture of bodied oil products from drying fatty oils, the 2- step process which comprises first producing a thickened bodied oil containing dispersed therein an alkali metal soap of the fatty acids of a drying oil by heating a mixture of said fatty oil and said soap to at least 200 C. and then vulcanizing said thickened bodied oil with sulphur in the presence of an organic vulcanization accelerator thereby producing said bodied oil products.

26. As an improvement in the manufacture of vulcanized bodied oil products useful as rubber substitutes, varnish ingredients and the like from fatty oils, the improvement which comprises substantially bodying the fatty oil, prior to vulcanization, by mixing 100 parts of said oil with 2 to 10 parts of a soap and heating the mixture to at least 200 0.

27. As an improvement in the manufacture of vulcanized bodied oil products from fatty oils, the

ing the fatty oil, prior to vulcanization, by means of heat in the presence of a soap, the amount of soap, temperature and time of heating being sufficient to substantially body said oil, said temperatures being at least 200 C., thus producing vulcanized bodied oil products having a greater body.

28. The process of claim 1 wherein said soap is a soap of an alkaline earth metal. a

29. The process of claim 1 wherein said fatty oil is a thickened, modified fatty oil, thickened and modified prior to admixture with said soap. 30. The process of claim 16 wherein said fatty oil is a thickened, modified fatty oil.

miszn AUER. LAJOS SUSZ'I'IEIK.

, improvement which comprises substantially body- 

